JPH0762254A - Polymer emulsion composition and polymer flocculant - Google Patents
Polymer emulsion composition and polymer flocculantInfo
- Publication number
- JPH0762254A JPH0762254A JP23728393A JP23728393A JPH0762254A JP H0762254 A JPH0762254 A JP H0762254A JP 23728393 A JP23728393 A JP 23728393A JP 23728393 A JP23728393 A JP 23728393A JP H0762254 A JPH0762254 A JP H0762254A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- water
- weight
- polymer emulsion
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 161
- 239000000839 emulsion Substances 0.000 title claims abstract description 97
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000004815 dispersion polymer Substances 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 claims 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 26
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- -1 dimethylaminoethyl Chemical group 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 229920006317 cationic polymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920006318 anionic polymer Polymers 0.000 description 6
- 239000008394 flocculating agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- SSZXAJUPVKMUJH-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;hydrochloride Chemical compound Cl.CN(C)CCOC(=O)C=C SSZXAJUPVKMUJH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- PMKQSEYPLQIEAY-YWNRKNDBSA-N Phaseolic acid Chemical compound OC(=O)C[C@@H](C(O)=O)OC(=O)\C=C\C1=CC=C(O)C(O)=C1 PMKQSEYPLQIEAY-YWNRKNDBSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CEJFYGPXPSZIID-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClCC1=CC=CC=C1.CN(C)CCOC(=O)C=C CEJFYGPXPSZIID-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JCRDPEHHTDKTGB-UHFFFAOYSA-N dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound Cl.CN(C)CCOC(=O)C(C)=C JCRDPEHHTDKTGB-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PMKQSEYPLQIEAY-UHFFFAOYSA-N trans-caffeoyl-L-malic acid Natural products OC(=O)CC(C(O)=O)OC(=O)C=CC1=CC=C(O)C(O)=C1 PMKQSEYPLQIEAY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高分子エマルジョン組成
物およびそれを主成分とする高分子凝集剤に関するもの
であり、さらに詳しくは排水処理用の凝集剤、脱水剤或
いは製紙用歩留まり向上剤、濾水性向上剤などの用途に
使用される新規な高分子エマルジョン組成物およびそれ
を主成分とする高分子凝集剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer emulsion composition and a polymer flocculant containing the same as a main component, and more specifically to a flocculant for treating waste water, a dehydrating agent or a yield improving agent for papermaking, The present invention relates to a novel polymer emulsion composition used for applications such as a drainage improver and a polymer flocculant containing the same as a main component.
【０００２】[0002]
【従来の技術】従来、排水処理用の凝集剤、脱水剤或は
製紙用歩留まり向上剤、濾水性向上剤等の用途に対し、
高分子凝集剤が広く用いられてきた。その製品形態は、
従来の粉末状型に加え、近年その取扱性の良さから油中
水型高分子凝集剤或は水溶性重合体分散型高分子凝集剤
などが注目され、多くの提案がなされ、利用されてい
る。例えば、特公昭５４−３７９８６号公報には、単量
体水溶液３０〜７０重量％と疎水性有機液体７０〜３０
重量％を界面活性剤を用いて乳化分散させ、油中水型ポ
リマーエマルジョンを得る方法が、特開平２−１０５８
０９号公報には、ジメチルアミノエチル（メタ）アクリ
レートを炭素数４〜１０の脂肪族ハライドまたは芳香族
ハライドで四級化した単量体を用い、重合体を溶解しな
い無機塩水溶液中で、かつこの塩水溶液に溶解可能なカ
チオン性重合体からなる分散剤の共存下で重合して水溶
性重合体分散型を得る方法等が提案されている。2. Description of the Related Art Conventionally, for applications such as coagulants for wastewater treatment, dehydrating agents, retention aids for papermaking, drainage improvers, etc.
Polymeric flocculants have been widely used. The product form is
In addition to the conventional powder type, in recent years, water-in-oil type polymer flocculants or water-soluble polymer dispersion type polymer flocculants have attracted attention due to their good handling properties, and many proposals have been made and used. . For example, Japanese Patent Publication No. 54-37986 discloses a monomer aqueous solution of 30 to 70% by weight and a hydrophobic organic liquid 70 to 30.
A method for obtaining a water-in-oil type polymer emulsion by emulsifying and dispersing wt% by using a surfactant is disclosed in JP-A-2-1058.
No. 09, a dimethylaminoethyl (meth) acrylate is used with a monomer obtained by quaternizing an aliphatic halide or an aromatic halide having 4 to 10 carbon atoms in an aqueous solution of an inorganic salt that does not dissolve the polymer, and There has been proposed a method of polymerizing in the presence of a dispersant composed of a cationic polymer which can be dissolved in this salt aqueous solution to obtain a water-soluble polymer dispersion type.
【０００３】これらの高分子凝集剤を使用に供するため
には、高分子凝集剤は通常タンクに貯蔵されるが、粉末
状型では通常０．１〜５．０重量％水溶液で、油中水型
ポリマーエマルジョン及び水溶性重合体分散型では製品
原液で、各々貯蔵される。しかし、これらの高分子凝集
剤は長期間貯蔵すると、ポリマー粒子の沈降及び再凝
集、増粘或は減粘等の粘度変化が生じるので、経時安定
性、保存安定性などに問題がある。とりわけ、近年、油
中水型ポリマーエマルジョンの使用が増加しているの
で、長期間タンク貯蔵での経時安定性、保存安定性が重
要になってきている。In order to use these polymer flocculants for use, the polymer flocculants are usually stored in a tank, but in the powder form, they are usually 0.1 to 5.0% by weight aqueous solution and water in oil. In the case of type polymer emulsion and water-soluble polymer dispersion type, they are stored as undiluted product solutions, respectively. However, when these polymer flocculants are stored for a long period of time, polymer particles are precipitated and re-aggregated, and viscosity changes such as thickening or thinning occur, so that there are problems in stability over time, storage stability and the like. In particular, since the use of water-in-oil type polymer emulsions has increased in recent years, stability over time and storage stability in long-term tank storage have become important.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、排水
処理用の凝集剤、脱水剤或いは製紙用歩留まり向上剤、
濾水性向上剤などの用途に使用することができる高分子
エマルジョン組成物であって、しかも長期間タンク貯蔵
しても、ポリマー粒子の沈降や再凝集がなく、また増粘
或は減粘等の粘度変化が生ぜず、経時安定性、保存安定
性に優れる高分子エマルジョン組成物を提供することで
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a coagulant for treating waste water, a dehydrating agent, or a yield improving agent for papermaking,
A polymer emulsion composition that can be used for applications such as a drainage improver, and does not cause sedimentation or re-aggregation of polymer particles even when stored in a tank for a long period of time. It is an object of the present invention to provide a polymer emulsion composition which does not cause a viscosity change and is excellent in stability over time and storage stability.
【０００５】[0005]
【課題を解決するための手段】本発明者は上記に鑑みこ
れらの課題を解決するため鋭意検討した結果、特定の油
中水型ポリマーエマルジョン、水溶性ポリマー水溶液お
よび／または水溶性ポリマー分散液、および無機塩を特
定量配合した液状の高分子エマルジョン組成物が、流動
性・経時安定性・保存安定性が良好であり、かつ高分子
凝集剤としての充分な性能を有することを見いだし本発
明を完成するに到った。In view of the above, the present inventor has conducted extensive studies to solve these problems, and as a result, a specific water-in-oil polymer emulsion, a water-soluble polymer aqueous solution and / or a water-soluble polymer dispersion liquid, The present invention has found that a liquid polymer emulsion composition in which a specific amount of an inorganic salt is blended has good fluidity, stability over time, storage stability, and sufficient performance as a polymer flocculant. It came to completion.
【０００６】本発明の請求項１の発明は、 （１）下記油中水型ポリマーエマルジョン（Ａ） ５０〜９９重量％、 （２）下記ポリマー水溶液（Ｂ）および／または下記水溶性ポリマー分散液（Ｃ ） １〜５０重量％、 および （３）硫酸アンモニウム、硫酸ナトリウム、リン酸二水素ナトリウム、塩化ナト リウムあるいはこれらの無機塩の二種類以上の混合物から選ばれる無機塩 ０．１〜２０重量％ からなる液状の高分子エマルジョン組成物である。 （Ａ）油中水型ポリマーエマルジョン； 一般式（ａ）（化３）The invention of claim 1 of the present invention is (1) 50 to 99% by weight of the following water-in-oil polymer emulsion (A), (2) the following aqueous polymer solution (B) and / or the following water-soluble polymer dispersion liquid: (C) 1 to 50% by weight, and (3) inorganic salt selected from ammonium sulfate, sodium sulfate, sodium dihydrogen phosphate, sodium chloride or a mixture of two or more of these inorganic salts 0.1 to 20% by weight. Is a liquid polymer emulsion composition. (A) Water-in-oil polymer emulsion; General formula (a)
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】（式中、Ａは酸素原子またはＮＨ；Ｚは炭
素数１〜４のアルキレン基または炭素数２〜４のヒドロ
キシアルキレン基；Ｒ1 は水素またはメチル基；Ｒ2 は
炭素数１〜４のアルキル基またはベンジル基；Ｒ3 、Ｒ
4 はそれぞれ独立に炭素数１〜４のアルキル基または炭
素数２〜４のヒドロキシアルキル基；Ｘ- は塩を形成す
る陰イオンを表す）で表されるカチオン性ビニル単量
体、または（メタ）アクリルアミド、Ｎ−Ｎ′−ジメチ
ル（メタ）アクリルアミド、アクリルニトリル、メチル
メタアクリレートから選ばれるノニオン性ビニル単量
体、または（メタ）アクリル酸、２−アクリルアミド−
２−メチルプロパンスルホン酸またはそれらの塩から選
ばれるアニオン性ビニル単量体を、水、疎水性有機液
体、界面活性剤の存在下で単独重合、またはこれらのビ
ニル単量体の二種以上を共重合させて得られる油中水型
ポリマーエマルジョンであって、ポリマーの濃度が２０
〜７０重量％、疎水性有機液体の濃度が１０〜５０重量
％、界面活性剤の濃度が８重量％以下である油中水型ポ
リマーエマルジョン。(In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 1 carbon atoms. 4 alkyl group or benzyl group; R 3 , R
4 are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms; X − represents a cationic anion forming a salt), or ) Acrylamide, N-N'-dimethyl (meth) acrylamide, acrylonitrile, a nonionic vinyl monomer selected from methylmethacrylate, or (meth) acrylic acid, 2-acrylamide-
Anionic vinyl monomers selected from 2-methylpropanesulfonic acid or salts thereof are homopolymerized in the presence of water, a hydrophobic organic liquid or a surfactant, or two or more of these vinyl monomers are polymerized. A water-in-oil polymer emulsion obtained by copolymerization, wherein the polymer concentration is 20
A water-in-oil polymer emulsion having a hydrophobic organic liquid concentration of 10 to 50% by weight and a surfactant concentration of 8% by weight or less.
【０００９】（Ｂ）ポリマー水溶液；（メタ）アクリル
アミド、Ｎ−Ｎ′−ジメチル（メタ）アクリルアミド、
アクリルニトリル、メチルメタアクリレート等のノニオ
ン性ビニル単量体、（メタ）アクリル酸、２−アクリル
アミド−２−メチルプロパンスルホン酸またはそれらの
塩から選ばれるアニオン性ビニル単量体、または上記一
般式（ａ）で表されるカチオン性ビニル単量体を、単独
重合するか、またはこれらビニル単量体の二種以上を共
重合させて得られる水溶性ポリマーを、水溶液中に０．
１〜１０重量％含有するポリマー水溶液。(B) Polymer aqueous solution; (meth) acrylamide, NN'-dimethyl (meth) acrylamide,
Nonionic vinyl monomers such as acrylonitrile and methylmethacrylate, anionic vinyl monomers selected from (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or salts thereof, or the above general formula ( The water-soluble polymer obtained by homopolymerizing the cationic vinyl monomer represented by a) or copolymerizing two or more of these vinyl monomers is added to an aqueous solution of 0.
An aqueous polymer solution containing 1 to 10% by weight.
【００１０】（Ｃ）水溶性ポリマー水分散液； 一般式（ｂ）（化４）(C) Water-soluble polymer water dispersion; General formula (b)
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】（式中、Ａは酸素原子またはＮＨ；Ｚは炭
素数１〜４のアルキレン基または炭素数２〜４のヒドロ
キシアルキレン基；Ｒ1 は水素またはメチル基；Ｒ2 、
Ｒ4 はメチル基またはエチル基；Ｒ3 は（ＣＨ2 ）n Ｃ
Ｈ3 （ｎは３〜９）またはＣ2Ｈ4 Ｃ6 Ｈ5 ；Ｘ- は塩
を形成する陰イオンを表す）で表されるカチオン性ビニ
ル単量体の単独重合、またはこれらカチオン性ビニル単
量体の一種あるいは二種以上と（メタ）アクリルアミド
との共重合を、生成する重合体を溶解しない無機塩水溶
液中で、かつこの無機塩水溶液に溶解可能な上記一般式
（ａ）で表されるカチオン性ビニル単量体から誘導され
るカチオン性水溶性重合体分散剤の共存下で行って得ら
れる水溶性ポリマーを１〜３０重量％含有する水溶性ポ
リマー水分散液。(Wherein A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 ,
R 4 is a methyl group or an ethyl group; R 3 is (CH 2 ) n C
Homopolymerization of a cationic vinyl monomer represented by H 3 (n is 3 to 9) or C 2 H 4 C 6 H 5 ; X − represents an anion that forms a salt, or a cationic vinyl monomer thereof. The copolymerization of one or more monomers with (meth) acrylamide is represented by the above general formula (a), which is soluble in an aqueous solution of an inorganic salt that does not dissolve the resulting polymer. A water-soluble polymer aqueous dispersion containing 1 to 30% by weight of a water-soluble polymer obtained by coexisting with a cationic water-soluble polymer dispersant derived from a cationic vinyl monomer.
【００１３】本発明の請求項２の発明は、請求項１に記
載の高分子エマルジョン組成物を主成分とする高分子凝
集剤である。The invention of claim 2 of the present invention is a polymer flocculant containing the polymer emulsion composition of claim 1 as a main component.
【００１４】すなわち本発明は、通常、油中水型ポリマ
ーエマルジョンとポリマー水溶液とを混合した組成物
は、瞬時に油中水型ポリマーエマルジョンが相転位して
ゲル状の高粘性液となるが、組成物全体に対して重量組
成で、油中水型ポリマーエマルジョンが５０〜９９重量
％、好ましくは７０〜９５重量％、水溶性ポリマーを
０．１〜１０重量％含有するポリマー水溶液が１〜５０
重量％、好ましくは５〜２５重量％、無機塩が０．１〜
２０重量％、好ましくは１〜１０重量％とすると、油中
水型ポリマーエマルジョンとポリマー水溶液が混じり合
い、ポリマー粒子の沈降及び再凝集がなく、流動性があ
り、かつ保存安定性の良い高分子ポリマー組成物が得ら
れることを見いだして成されたものである。That is, according to the present invention, a composition in which a water-in-oil type polymer emulsion and an aqueous polymer solution are mixed is usually a water-in-oil type polymer emulsion which undergoes a phase transition instantaneously to form a gel-like highly viscous liquid. The composition of the water-in-oil polymer emulsion is 50 to 99% by weight, preferably 70 to 95% by weight, and the aqueous polymer solution containing the water-soluble polymer is 0.1 to 10% by weight based on the total weight of the composition.
% By weight, preferably 5 to 25% by weight, 0.1% inorganic salt
When the amount is 20% by weight, preferably 1 to 10% by weight, the water-in-oil type polymer emulsion and the aqueous polymer solution are mixed with each other, there is no sedimentation and re-aggregation of polymer particles, and the polymer is fluid and has good storage stability. It was made by finding that a polymer composition can be obtained.
【００１５】あらかじめ無機塩が含有されている水溶性
ポリマー水分散液を用いて油中水型ポリマーエマルジョ
ンと混合して組成物を作る場合は、必要に応じ更に無機
塩を添加して組成物全体に対し無機塩が０．１〜２０重
量％、好ましくは１．０〜１０重量％となるようにする
ことが必要であり、そうすることにより、流動性があり
保存安定性が良く、かつ充分な性能を有する高分子エマ
ルジョン組成物が得られる。When a composition is prepared by mixing an aqueous dispersion of a water-soluble polymer containing an inorganic salt in advance with a water-in-oil type polymer emulsion, an inorganic salt is further added, if necessary. On the other hand, it is necessary to adjust the content of the inorganic salt to 0.1 to 20% by weight, preferably 1.0 to 10% by weight. By doing so, it has fluidity, good storage stability, and sufficient A polymer emulsion composition having various properties can be obtained.
【００１６】本発明の高分子エマルジョン組成物中の、
油中水型ポリマーエマルジョンの重量組成が５０重量％
以下の場合は組成物の流動性が悪くなり、９９重量％以
上の場合は保存安定性が悪くなり好ましくない。又、ポ
リマー水溶液および／または水溶性ポリマー分散液の重
量組成が５０重量％以上の場合は、組成物の流動性およ
び保存安定性が悪くなり好ましくない。又、無機塩が
０．１重量％以下の場合は、組成物の流動性が悪くな
り、２０重量％以上の場合は、無機塩の析出等が起こる
ので好ましくない。In the polymer emulsion composition of the present invention,
The weight composition of the water-in-oil type polymer emulsion is 50% by weight.
In the following cases, the fluidity of the composition will be poor, and in the case of 99% by weight or more, the storage stability will be poor, which is not preferable. If the weight composition of the aqueous polymer solution and / or the water-soluble polymer dispersion is 50% by weight or more, the fluidity and storage stability of the composition deteriorate, which is not preferable. Further, when the content of the inorganic salt is 0.1% by weight or less, the fluidity of the composition is deteriorated, and when it is 20% by weight or more, precipitation of the inorganic salt or the like occurs, which is not preferable.
【００１７】また、本発明の高分子エマルジョン組成物
が、イオン性が異なる油中水型ポリマーエマルジョンと
ポリマー水溶液または水溶性ポリマー水分散液との組成
物である場合には、異イオン性のため組成比によって
は、カチオン／アニオンの複合体が生成し、エマルジョ
ン粒子の破壊が起こることが予想されたが、実際はエマ
ルジョン粒子の破壊はなく、流動性があり、かつ保存安
定性の良い高分子エマルジョン組成物が得られた。Further, when the polymer emulsion composition of the present invention is a composition of a water-in-oil type polymer emulsion having different ionic properties and a polymer aqueous solution or a water-soluble polymer aqueous dispersion, it is Depending on the composition ratio, it was expected that a cation / anion complex would be formed and the emulsion particles would be destroyed, but in reality, there was no emulsion particle destruction, and the polymer emulsion was fluid and had good storage stability. A composition was obtained.
【００１８】本発明で用いる油中水型ポリマーエマルジ
ョンは、ポリマー濃度が２０〜７０重量％、好ましくは
３０〜５０重量％、疎水性有機液体の濃度が１０〜５０
重量％、好ましくは２５〜４０重量％、界面活性剤濃度
が８重量％以下、好ましくは２〜６重量％である。ポリ
マー濃度が７０重量％以上の場合は、保存安定性が悪く
なり、２０重量％以下の場合は、ポリマーの分子量が低
くなり高分子凝集剤としての性能が充分でなく好ましく
ない。The water-in-oil type polymer emulsion used in the present invention has a polymer concentration of 20 to 70% by weight, preferably 30 to 50% by weight, and a hydrophobic organic liquid concentration of 10 to 50%.
% By weight, preferably 25 to 40% by weight, and the surfactant concentration is 8% by weight or less, preferably 2 to 6% by weight. When the polymer concentration is 70% by weight or more, the storage stability becomes poor, and when it is 20% by weight or less, the polymer has a low molecular weight and the performance as a polymer flocculant is not sufficient, which is not preferable.
【００１９】疎水性液体の濃度が、１０重量％以下の場
合は保存安定性が悪くなり、５０重量％以上の場合は、
流動性、保存安定性に大きな向上がなく、経済的にもコ
ストアップになるため５０重量％以下で良い。界面活性
剤濃度が８重量％以上の場合は、流動性が悪くなり好ま
しくない。When the concentration of the hydrophobic liquid is 10% by weight or less, the storage stability becomes poor, and when it is 50% by weight or more,
Since the fluidity and storage stability are not greatly improved and the cost is economically increased, the content is preferably 50% by weight or less. When the surfactant concentration is 8% by weight or more, the fluidity is deteriorated, which is not preferable.
【００２０】又、本発明で用いるポリマー水溶液は、水
溶性ポリマーを水溶液中に０．１〜１０重量％、好まし
くは０．１〜５重量％含有する。１０重量％以上の場
合、ポリマー水溶液が高粘性となり取扱上好ましくな
く、０．１重量％以下の場合はポリマー濃度が低くなり
実用的でない。又、本発明で用いる水溶性ポリマー分散
液は、水溶性ポリマーを１０〜３０重量％、好ましくは
１０〜２０重量％含有する。３０重量％以上の場合は、
流動性、保存安定性が悪くなり好ましくない。The aqueous polymer solution used in the present invention contains a water-soluble polymer in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight. When it is 10% by weight or more, the polymer aqueous solution becomes highly viscous, which is not preferable in handling, and when it is 0.1% by weight or less, the polymer concentration becomes low, which is not practical. The water-soluble polymer dispersion used in the present invention contains the water-soluble polymer in an amount of 10 to 30% by weight, preferably 10 to 20% by weight. In case of 30% by weight or more,
It is not preferable because the fluidity and storage stability deteriorate.
【００２１】本発明で用いる無機塩としては、硫酸アン
モニウム、硫酸ナトリウム、リン酸二水素ナトリウム、
塩化ナトリウム等の無機アニオン塩、或はこれらの塩の
二種類以上混合したものが挙げられる。これらの塩以外
でも、油中水型ポリマーの相転位を生じさせず、かつ水
溶性のものならば使用することができる。The inorganic salts used in the present invention include ammonium sulfate, sodium sulfate, sodium dihydrogen phosphate,
Examples thereof include inorganic anion salts such as sodium chloride, or a mixture of two or more of these salts. Other than these salts, those which do not cause phase transition of the water-in-oil type polymer and are water-soluble can be used.
【００２２】疎水性有機液体としては、灯油、軽油、ヘ
キサン、イソパラフィン、ベンゼン、トルエン等の脂肪
族炭化水素または芳香族炭化水素等が挙げられる。Examples of the hydrophobic organic liquid include kerosene, light oil, hexane, isoparaffin, benzene, toluene and other aliphatic hydrocarbons or aromatic hydrocarbons.
【００２３】界面活性剤としては、ソルビタンモノステ
アレート、ソルビタンモノオレエート等のソルビタン脂
肪族エステル、ステアリン酸モノグリセリド、ステアリ
ン酸モノジグリセリド、オレイン酸モノジグリセリド等
のグリセリン脂肪酸エステルまたは２種以上の混合物、
ポリオキシエチレンソルビタンモノオレエート、ポリオ
キシエチレンラウリルエーテル、ポリオキシエチレンソ
ルビタントリステアレート、ポリエチレングリコールモ
ノオレエート等の非イオン界面活性剤が挙げられる。As the surfactant, sorbitan monostearate, sorbitan monooleate and other sorbitan aliphatic esters, stearic acid monoglyceride, stearic acid monodiglyceride, oleic acid monodiglyceride and other glycerin fatty acid esters, or a mixture of two or more thereof,
Nonionic surfactants such as polyoxyethylene sorbitan monooleate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan tristearate, polyethylene glycol monooleate and the like can be mentioned.
【００２４】上記一般式（ａ）で表されるカチオン性ビ
ニル単量体としては、ジメチルアミノエチル（メタ）ア
クリレート、ジエチルアミノエチル（メタ）アクリレー
ト、ジメチルアミノヒドロキシ（メタ）アクリレート等
のようなジアルキルアミノ（ヒドロキシ）アルキル（メ
タ）アクリレートの中和塩または四級化物、ジメチルア
ミノエチル（メタ）アクリルアミド、ジメチルアミノヒ
ドロキシプロピル（メタ）アクリルアミド等のようなジ
アルキルアミノ（ヒドロキシ）アルキル（メタ）アクリ
ルアミドの中和塩または四級化物等が挙げられる。Examples of the cationic vinyl monomer represented by the above general formula (a) include dialkylamino such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminohydroxy (meth) acrylate. Neutralization salts of (hydroxy) alkyl (meth) acrylates or quaternary compounds, dialkylamino (hydroxy) alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminohydroxypropyl (meth) acrylamide, etc. Examples thereof include salts and quaternary compounds.
【００２５】また、上記一般式（ｂ）で表されるカチオ
ン性ビニル単量体としては、ジメチルアミノエチル（メ
タ）アクリレート、ジエチルアミノエチル（メタ）アク
リレート、ジメチルアミノヒドロキシ（メタ）アクリレ
ート等のようなジアルキルアミノ（ヒドロキシ）アルキ
ル（メタ）アクリレートを炭素数４〜１０のアルキルハ
ライドまたは２−ハロエチルベンゼンで四級化したもの
が挙げられる。Examples of the cationic vinyl monomer represented by the above general formula (b) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminohydroxy (meth) acrylate and the like. Examples thereof include those obtained by quaternizing dialkylamino (hydroxy) alkyl (meth) acrylate with an alkyl halide having 4 to 10 carbon atoms or 2-haloethylbenzene.
【００２６】[0026]
【作用】本発明の高分子エマルジョン組成物の特徴は、
無機塩の作用により、油中水型ポリマーエマルジョン
と、ポリマー水溶液および／または水溶性ポリマー水分
散液が混ざり合い、流動性かつ保存安定の良い高分子エ
マルジョン組成物となることにある。すなわち、無機塩
は組成物中のポリマーを微粒子状態で、かつ均一に分散
させる作用ないしは溶解させない作用があり、ポリマー
粒子は組成物中で微粒子状でかつ均一に分散する。更
に、無機塩は油中水型ポリマーエマルジョン中の疎水性
有機液体を水中油型エマルジョン粒子とする作用があ
る。従って、疎水性有機液体はエマルジョン微粒子とな
って、均一に分散しているポリマー粒子間に混じり込む
ため、ポリマー粒子の沈降或は凝集が防止され、保存安
定性が良く流動性の良い組成物となるものと考えられ
る。The function of the polymer emulsion composition of the present invention is as follows.
Due to the action of the inorganic salt, the water-in-oil type polymer emulsion is mixed with the aqueous polymer solution and / or the water-soluble polymer aqueous dispersion to form a polymer emulsion composition having good fluidity and good storage stability. That is, the inorganic salt has the function of uniformly dispersing or not dissolving the polymer in the composition in the form of fine particles, and the polymer particles are finely dispersed in the composition in a uniform manner. Further, the inorganic salt acts to convert the hydrophobic organic liquid in the water-in-oil type polymer emulsion into oil-in-water emulsion particles. Therefore, since the hydrophobic organic liquid becomes emulsion fine particles and mixes between the polymer particles that are uniformly dispersed, sedimentation or aggregation of the polymer particles is prevented, and the composition has good storage stability and good fluidity. It is supposed to be.
【００２７】[0027]
【実施例】以下実施例を挙げて本発明を具体的に説明す
るが、本発明はその主旨を越えない限り以下の実施例に
限定されるものではない。 （油中水型ポリマーエマルジョンの製造）本発明に用い
られる油中水型ポリマーエマルジョンは、公知の方法、
すなわち特公昭５４−３７９８６号公報、特公昭５２−
３９４１７号公報等に記載の方法に準じ、以下の油中水
型カチオン性ポリマーエマルジョン（Ａ）、（Ｂ）、油
中水型アニオン性ポリマーエマルジョン（Ｃ）、（Ｄ）
を製造した。油相にＮ−ヘキサンを用い、ジメチルアミ
ノエチルメタアクリレート塩酸塩とアクリルアミドを共
重合比３０対７０（モル）で共重合して全エマルジョン
に対し、ポリマー濃度が４０．０重量％、油相が３０．
０重量％の油中水型カチオン性ポリマーエマルジョンを
製造した。この油中水型カチオン性ポリマーエマルジョ
ンを（Ａ）とする。EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. (Production of Water-in-oil Polymer Emulsion) The water-in-oil polymer emulsion used in the present invention can be produced by a known method.
That is, Japanese Patent Publication No. 54-37986 and Japanese Patent Publication No. 52-
According to the method described in Japanese Patent No. 39417, etc., the following water-in-oil type cationic polymer emulsions (A) and (B), water-in-oil type anionic polymer emulsions (C) and (D) are described.
Was manufactured. N-hexane was used for the oil phase, dimethylaminoethyl methacrylate hydrochloride and acrylamide were copolymerized at a copolymerization ratio of 30:70 (mol), and the polymer concentration was 40.0% by weight, and the oil phase was 30.
A 0 wt% water-in-oil cationic polymer emulsion was prepared. This water-in-oil type cationic polymer emulsion is designated as (A).
【００２８】ジメチルアミノエチルアクリレート塩酸塩
とアクリルアミドの共重合比を、６０対４０（モル）に
変更した以外は油中水型カチオン性ポリマーエマルジョ
ン（Ａ）と同様にして製造した。この油中水型カチオン
性ポリマーエマルジョンを（Ｂ）とする。A water-in-oil type cationic polymer emulsion (A) was prepared in the same manner as above except that the copolymerization ratio of dimethylaminoethyl acrylate hydrochloride and acrylamide was changed to 60:40 (mol). This water-in-oil type cationic polymer emulsion is designated as (B).
【００２９】油相にアイソパー（エクソン社、イソパラ
フィン）を用い、アクリル酸とアクリルアミドを共重合
比２０対８０（モル）で共重合して全エマルジョンに対
し、ポリマー濃度が３０．０重量％、油相が２８．０重
量％の油中水型アニオン性ポリマーエマルジョンを製造
した。この油中水型アニオン性ポリマーエマルジョンを
（Ｃ）とする。Isopar (Exxon Co., isoparaffin) was used for the oil phase, and acrylic acid and acrylamide were copolymerized at a copolymerization ratio of 20:80 (mol) to give a total polymer concentration of 30.0% by weight and an oil. A water-in-oil anionic polymer emulsion with a phase of 28.0% by weight was prepared. This water-in-oil type anionic polymer emulsion is referred to as (C).
【００３０】アクリル酸とアクリルアミドの共重合比を
４０対６０（モル）に変更した以外は油中水型アニオン
性ポリマーエマルジョン（Ｃ）と同様にして製造した。
この油中水型アニオン性ポリマーエマルジョンを（Ｄ）
とする。A water-in-oil type anionic polymer emulsion (C) was prepared except that the copolymerization ratio of acrylic acid and acrylamide was changed to 40:60 (mol).
This water-in-oil type anionic polymer emulsion (D)
And
【００３１】（ポリマー水溶液の製造）本発明に用いら
れるポリマー水溶液のポリマーは、常法により得られた
粉末のポリマーである。すなわち重合するモノマーを水
に溶解し一般的に使用される重合開始剤を加え重合し、
脱水、粉末状としたポリマーである。このようにして以
下のカチオン性ポリマー水溶液（Ｅ）、アニオン性ポリ
マー水溶液（Ｆ）を製造した。ジメチルアミノエチルア
クリレート塩酸塩とアクリルアミドを共重合比５０対５
０（モル）で共重合して得られた粉末状のポリマーを、
純水に溶解し０．２重量％水溶液とした。このポリマー
水溶液を（Ｅ）とする。(Production of Polymer Aqueous Solution) The polymer of the polymer aqueous solution used in the present invention is a powdery polymer obtained by a conventional method. That is, a monomer to be polymerized is dissolved in water and a polymerization initiator generally used is added and polymerized,
It is a dehydrated and powdered polymer. Thus, the following cationic polymer aqueous solution (E) and anionic polymer aqueous solution (F) were produced. Copolymerization ratio of dimethylaminoethyl acrylate hydrochloride and acrylamide 50: 5
The powdery polymer obtained by copolymerization with 0 (mol) is
It was dissolved in pure water to obtain a 0.2 wt% aqueous solution. Let this polymer aqueous solution be (E).
【００３２】アクリル酸とアクリルアミドを共重合比３
０対７０（モル）で共重合して得られた粉末状のポリマ
ーを用いた以外はポリマー水溶液（Ｅ）と同様にしてポ
リマー水溶液を製造した。このポリマー水溶液を（Ｆ）
とする。Copolymerization ratio of acrylic acid and acrylamide 3
An aqueous polymer solution was produced in the same manner as the aqueous polymer solution (E) except that a powdery polymer obtained by copolymerizing 0:70 (mol) was used. This polymer aqueous solution (F)
And
【００３３】（水溶性ポリマー水分散液の製造）本発明
に用いられる水溶性ポリマー水分散液は、公知の方法す
なわち特開平２−１０５８０９号公報等に記載の方法に
準じ製造した。又この分散液製造時に使用されるカチオ
ン性水溶性重合体分散剤は、常法により得た粉末状カチ
オン性ポリマーである。このようにして次の水溶性ポリ
マー水分散液（Ｇ）を製造した。ジメチルブチルアミノ
エチルアクリレート塩酸塩とアクリルアミドを共重合比
５０対５０（モル）で共重合して、ポリマー濃度が２
０．０重量％、分散剤のジメチルアミノエチルアクリレ
ート塩酸塩から誘導されるカチオン性水溶性重合体及び
硫酸アンモニウムが各々０．５重量％、２０．０重量％
の水溶性ポリマー分散液を製造した。この水溶性ポリマ
ー分散液を（Ｇ）とする。(Production of Water-Soluble Polymer Aqueous Dispersion) The water-soluble polymer aqueous dispersion used in the present invention was produced according to a known method, that is, a method described in JP-A-2-105809. The cationic water-soluble polymer dispersant used in the production of this dispersion is a powdery cationic polymer obtained by a conventional method. Thus, the following water-soluble polymer aqueous dispersion (G) was produced. Dimethylbutylaminoethyl acrylate hydrochloride and acrylamide were copolymerized at a copolymerization ratio of 50:50 (mol) to give a polymer concentration of 2
0.0% by weight, 0.5% by weight of a cationic water-soluble polymer derived from dimethylaminoethyl acrylate hydrochloride as a dispersant and 20.0% by weight of ammonium sulfate, respectively.
A water-soluble polymer dispersion of was prepared. This water-soluble polymer dispersion is designated as (G).
【００３４】ジメチルアミノエチルアクリレートベンジ
ルクロライドとアクリルアミドを共重合比７０対３０
（モル）で共重合した以外は水溶性ポリマー分散液
（Ｇ）と同様にして水溶性ポリマー分散液を製造した。
この水溶性ポリマー水分散液を（Ｈ）とする。Copolymerization ratio of dimethylaminoethyl acrylate benzyl chloride and acrylamide 70:30
A water-soluble polymer dispersion liquid was produced in the same manner as the water-soluble polymer dispersion liquid (G) except that the copolymerization was carried out in (mol).
This water-soluble polymer aqueous dispersion is designated as (H).
【００３５】（実施例１）および（比較例１） ポリマー水溶液（Ｅ）中に、粉末状硫酸アンモニウムを
添加し、硫酸アンモニウム２０重量％含有ポリマー水溶
液を調整した。この硫酸アンモニウム含有ポリマー水溶
液を油中水型ポリマーエマルジョン（Ａ）に添加、攪拌
し、表１に示す配合の高分子エマルジョン組成物を作成
した。保存安定性を測定した結果を表１に示す。なお粘
度測定は、Ｂ型回転粘度計を使用し、３０℃、ローター
ＮＯ３、３０ｒｐｍの条件で実施した。(Example 1) and (Comparative Example 1) Powdery ammonium sulfate was added to the polymer aqueous solution (E) to prepare a polymer aqueous solution containing 20% by weight of ammonium sulfate. This ammonium sulfate-containing polymer aqueous solution was added to the water-in-oil polymer emulsion (A) and stirred to prepare a polymer emulsion composition having the formulation shown in Table 1. The results of measuring the storage stability are shown in Table 1. The viscosity was measured using a B type rotational viscometer under the conditions of 30 ° C., rotor NO3, and 30 rpm.
【００３６】[0036]
【表１】 [Table 1]
【００３７】（実施例２）および（比較例２） 油中水型ポリマーエマルジョン（Ｂ）、ポリマー水溶液
（Ｆ）及び硫酸アンモニウムを使用し表２に示す配合で
実施例１と同様にして高分子エマルジョン組成物を作製
した。保存安定性を測定した結果を表２に示す。(Example 2) and (Comparative Example 2) A polymer emulsion was prepared in the same manner as in Example 1 except that the water-in-oil type polymer emulsion (B), the aqueous polymer solution (F) and ammonium sulfate were used and the formulation shown in Table 2 was used. A composition was made. The results of measuring storage stability are shown in Table 2.
【００３８】[0038]
【表２】 [Table 2]
【００３９】（実施例３）および（比較例３） 油中水型ポリマーエマルジョン（Ｃ）、ポリマー水溶液
（Ｅ）及び硫酸アンモニウムを使用し表３に示す配合で
実施例１と同様にして高分子エマルジョン組成物を作製
した。保存安定性を測定した結果を表３に示す。(Example 3) and (Comparative Example 3) A polymer emulsion was prepared in the same manner as in Example 1 except that the water-in-oil type polymer emulsion (C), the aqueous polymer solution (E) and ammonium sulfate were used and the formulations shown in Table 3 were used. A composition was made. The results of measuring the storage stability are shown in Table 3.
【００４０】[0040]
【表３】 [Table 3]
【００４１】（実施例４）および（比較例４） 油中水型ポリマーエマルジョン（Ｄ）、ポリマー水溶液
（Ｆ）及び硫酸アンモニウムを使用し表４に示す配合で
実施例１と同様にして高分子エマルジョン組成物を作製
した。保存安定性を測定した結果を表４に示す。(Example 4) and (Comparative Example 4) A water-in-oil type polymer emulsion (D), an aqueous polymer solution (F) and ammonium sulfate were used and the composition shown in Table 4 was used. A composition was made. The results of measuring the storage stability are shown in Table 4.
【００４２】[0042]
【表４】 [Table 4]
【００４３】（実施例５）および（比較例５） 水溶性ポリマー分散液（Ｈ）に、粉末状硫酸ナトリウム
を添加し、無機塩（硫酸アンモニウム＋硫酸ナトリウ
ム）の合計が４０重量％含有水溶性ポリマー分散液を調
整した。この無機塩含有水溶性ポリマー分散液を油中水
型ポリマーエマルジョン（Ａ）に添加、攪拌し、表５に
示す配合高分子エマルジョン組成物を作製した。保存安
定性を測定した結果を表５に示す。硫酸ナトリウムは高
分子エマルジョン組成物を調整するとき、必要に応じて
水溶性ポリマー分散液に添加し、組成物全体に対し０．
１〜２０重量％となるように添加した。(Example 5) and (Comparative Example 5) Powdered sodium sulfate was added to the water-soluble polymer dispersion liquid (H), and the total amount of inorganic salts (ammonium sulfate + sodium sulfate) was 40% by weight. The dispersion was prepared. This inorganic salt-containing water-soluble polymer dispersion was added to the water-in-oil polymer emulsion (A) and stirred to prepare a compounded polymer emulsion composition shown in Table 5. The results of measuring the storage stability are shown in Table 5. Sodium sulphate is added to the water-soluble polymer dispersion, if necessary, when preparing a polymer emulsion composition, and is added to the total composition at 0.
It was added so as to be 1 to 20% by weight.
【００４４】[0044]
【表５】 [Table 5]
【００４５】（実施例６）および（比較例６） 油中水型ポリマーエマルジョン（Ｂ）、水溶性ポリマー
分散液（Ｇ）及び硫酸ナトリウムを使用し表６に示す配
合で実施例５と同様にして高分子エマルジョン組成物を
作製した。保存安定性を測定した結果を表６に示す。(Example 6) and (Comparative Example 6) A water-in-oil type polymer emulsion (B), a water-soluble polymer dispersion (G) and sodium sulfate were used, and the composition shown in Table 6 was used. To prepare a polymer emulsion composition. The results of measuring the storage stability are shown in Table 6.
【００４６】[0046]
【表６】 [Table 6]
【００４７】（実施例７）および（比較例７） 油中水型ポリマーエマルジョン（Ｃ）、水溶性ポリマー
分散液（Ｈ）及び硫酸ナトリウムを使用し表７に示す配
合で実施例５と同様にして高分子エマルジョン組成物を
作製した。保存安定性を測定した結果を表７に示す。(Example 7) and (Comparative Example 7) A water-in-oil type polymer emulsion (C), a water-soluble polymer dispersion (H) and sodium sulfate were used and blended as shown in Table 7 in the same manner as in Example 5. To prepare a polymer emulsion composition. The results of measuring the storage stability are shown in Table 7.
【００４８】[0048]
【表７】 [Table 7]
【００４９】（実施例８）および（比較例８） 油中水型ポリマーエマルジョン（Ｄ）、水溶性ポリマー
分散液（Ｇ）及び硫酸ナトリウムを使用し表８に示す配
合で実施例５と同様にして高分子エマルジョン組成物を
作製した。保存安定性を測定した結果を表８に示す。(Example 8) and (Comparative Example 8) A water-in-oil polymer emulsion (D), a water-soluble polymer dispersion (G) and sodium sulfate were used in the same composition as shown in Table 8 in the same manner as in Example 5. To prepare a polymer emulsion composition. The results of measuring the storage stability are shown in Table 8.
【００５０】[0050]
【表８】 [Table 8]
【００５１】（実施例９）紙パルプ排水の生物処理によ
り発生した余剰汚泥（ｐＨ：６．５、全ｓｓ濃度：２．
１６重量％）を使用し、本発明の高分子エマルジョン組
成物の高分子凝集剤としての性能を試験した。 １）高分子エマルジョン組成物として、表１中の実施例
１の１の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン９０重量％、ポリマー水溶液８重量％、硫
酸アンモニウム２重量％）を使用した。 ２）高分子エマルジョン組成物として、表２中の実施例
２の２の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン８０重量％、ポリマー水溶液１６重量％、
硫酸アンモニウム４重量％）を使用した。 ３）高分子エマルジョン組成物として、表５中の実施例
５の３の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン７０重量％、水溶性ポリマー分散液２４重
量％、硫酸ナトリウム６重量％）を使用した。(Example 9) Excess sludge (pH: 6.5, total ss concentration: 2.) generated by biological treatment of paper pulp wastewater.
(16% by weight) was used to test the performance of the polymeric emulsion composition of the present invention as a polymeric flocculant. 1) As the polymer emulsion composition, the polymer emulsion composition of 1 of Example 1 in Table 1 (90% by weight of water-in-oil type polymer emulsion, 8% by weight of polymer aqueous solution, 2% by weight of ammonium sulfate) was used. 2) As the polymer emulsion composition, the polymer emulsion composition of 2 of Example 2 in Table 2 (80% by weight of water-in-oil type polymer emulsion, 16% by weight of polymer aqueous solution,
Ammonium sulfate 4% by weight) was used. 3) As a polymer emulsion composition, the polymer emulsion composition of 3 in Example 5 in Table 5 (70% by weight of water-in-oil polymer emulsion, 24% by weight of water-soluble polymer dispersion, 6% by weight of sodium sulfate) It was used.
【００５２】性能テストは、余剰汚泥２００ｍｌとり、
これに高分子凝集剤０．１重量％水溶液を添加し、プロ
ペラ付き攪拌機を用いて５００ｒｐｍで９０秒攪拌し、
フロックを生成させた。フロックが生成した余剰汚泥ス
ラリーをヌッチエ濾過（１００メッシュナイロン濾布）
し３０秒後の濾液量を測定した。更に得られたフロック
を加圧脱水（１ｋｇ／ｃｍ2 、１分）し、フロックの含
水率を測定した。結果をまとめて表９に示す。For the performance test, 200 ml of excess sludge was taken,
A 0.1% by weight aqueous solution of a polymer flocculant was added thereto, and the mixture was stirred at 500 rpm for 90 seconds using a stirrer with a propeller,
Flock was generated. Excess sludge slurry generated by flocs is subjected to Nutchie filtration (100 mesh nylon filter cloth)
Then, the amount of filtrate after 30 seconds was measured. Further, the obtained flocs were dehydrated under pressure (1 kg / cm 2 , 1 minute), and the water content of the flocs was measured. The results are summarized in Table 9.
【００５３】[0053]
【表９】 [Table 9]
【００５４】（実施例１０）填料として対パルプ固形分
当たり１０重量％の酸化チタンを添加したパルプスラリ
ー（ＮＢＫＰ、濃度０．５重量％、ＣＳＦ：２１０ｍ
ｌ）を使用し、本発明の高分子エマルジョン組成物の保
留まり向上剤、濾水性向上剤としての性能評価を行っ
た。 １）高分子エマルジョン組成物として、表１中の実施例
１の１の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン９０重量％、ポリマー水溶液８重量％、硫
酸アンモニウム２重量％）を使用した。 ２）高分子エマルジョン組成物として、表２中の実施例
２の２の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン８０重量％、ポリマー水溶液１６重量％、
硫酸アンモニウム４重量％）を使用した。 ３）高分子エマルジョン組成物として、表５中の実施例
５の３の高分子エマルジョン組成物（油中水型ポリマー
エマルジョン７０重量％、水溶性ポリマー分散液２４重
量％、硫酸ナトリウム６重量％）を使用した。Example 10 Pulp slurry (NBKP, concentration 0.5% by weight, CSF: 210 m) to which 10% by weight of titanium oxide was added as a filler based on the solid content of pulp.
1) was used to evaluate the performance of the polymer emulsion composition of the present invention as a retention improver and a drainage improver. 1) As the polymer emulsion composition, the polymer emulsion composition of 1 of Example 1 in Table 1 (90% by weight of water-in-oil polymer emulsion, 8% by weight of polymer aqueous solution, 2% by weight of ammonium sulfate) was used. 2) As a polymer emulsion composition, the polymer emulsion composition of 2 of Example 2 in Table 2 (80% by weight of water-in-oil type polymer emulsion, 16% by weight of aqueous polymer solution,
Ammonium sulfate 4% by weight) was used. 3) As a polymer emulsion composition, the polymer emulsion composition of 3 of Example 5 in Table 5 (70% by weight of water-in-oil type polymer emulsion, 24% by weight of water-soluble polymer dispersion, 6% by weight of sodium sulfate) It was used.
【００５５】テストは、上記パルプスラリー１５００ｍ
ｌをとり、硫酸でｐＨ４．５に調整した後、高分子凝集
剤の０．１重量％水溶液を添加し、プロペラ羽根付き攪
拌機を用い５００ｒｐｍで６０秒攪拌し、フロックを生
成させた。次いでＤＤＪテスター（ＴＡＰＰＩスタンダ
ード、１００メシュ金網）を用いて、凝集したパルプス
ラリーを５００ｒｐｍで３０秒攪拌した後、濾過し、濾
液のｓｓ濃度を測定した。結果を表１０にまとめて示
す。The test was conducted with the above pulp slurry 1500 m.
After taking 1 liter, the pH was adjusted to 4.5 with sulfuric acid, a 0.1 wt% aqueous solution of a polymer flocculant was added, and the mixture was stirred at 500 rpm for 60 seconds using a stirrer with a propeller blade to generate flocs. Then, using a DDJ tester (TAPPI standard, 100 mesh wire mesh), the agglomerated pulp slurry was stirred at 500 rpm for 30 seconds and then filtered, and the ss concentration of the filtrate was measured. The results are summarized in Table 10.
【００５６】[0056]
【表１０】 [Table 10]
【００５７】表９および表１０の結果から、本発明の高
分子エマルジョン組成物は、従来高分子凝集剤として使
用されていた油中水型ポリマーエマルジョン（Ａ）、油
中水型ポリマーエマルジョン（Ｂ）、ポリマー水溶液
（Ｅ）、水溶性ポリマー分散液（Ｈ）と比較して同等ま
たは優れる性能を有していることが判った。From the results shown in Tables 9 and 10, the polymer emulsion composition of the present invention shows that the water-in-oil type polymer emulsion (A) and the water-in-oil type polymer emulsion (B) which were conventionally used as the polymer flocculant were used. ), An aqueous polymer solution (E), and a water-soluble polymer dispersion liquid (H), the same or superior performance was found.
【００５８】[0058]
【発明の効果】本発明の高分子エマルジョン組成物は長
期間タンク貯蔵しても、ポリマー粒子の沈降や再凝集が
なく、また増粘或は減粘等の粘度変化が生ぜず、経時安
定性や保存安定性に優れている。本発明の高分子エマル
ジョン組成物は排水処理用の凝集剤、脱水剤或いは製紙
用歩留まり向上剤、濾水性向上剤などの用途に使用する
ことができるのでその産業上の利用価値は甚だ大きい。The polymer emulsion composition of the present invention does not undergo sedimentation or re-aggregation of polymer particles even when stored in a tank for a long period of time, and does not cause a viscosity change such as thickening or thinning. It also has excellent storage stability. Since the polymer emulsion composition of the present invention can be used as a coagulant for wastewater treatment, a dehydrating agent, a retention aid for papermaking, a drainage improver, etc., its industrial utility value is extremely great.
Claims (2)
アルキレン基または炭素数２〜４のヒドロキシアルキレ
ン基；Ｒ1 は水素またはメチル基；Ｒ2 は炭素数１〜４
のアルキル基またはベンジル基；Ｒ3 、Ｒ4 はそれぞれ
独立に炭素数１〜４のアルキル基または炭素数２〜４の
ヒドロキシアルキル基；Ｘ- は塩を形成する陰イオンを
表す）で表されるカチオン性ビニル単量体、または（メ
タ）アクリルアミド、Ｎ−Ｎ′−ジメチル（メタ）アク
リルアミド、アクリルニトリル、メチルメタアクリレー
トから選ばれるノニオン性ビニル単量体、または（メ
タ）アクリル酸、２−アクリルアミド−２−メチルプロ
パンスルホン酸またはそれらの塩から選ばれるアニオン
性ビニル単量体を、水、疎水性有機液体、界面活性剤の
存在下で単独重合、またはこれらのビニル単量体の二種
以上を共重合させて得られる油中水型ポリマーエマルジ
ョンであって、ポリマーの濃度が２０〜７０重量％、疎
水性有機液体の濃度が１０〜５０重量％、界面活性剤の
濃度が８重量％以下である油中水型ポリマーエマルジョ
ン。 （Ｂ）ポリマー水溶液；（メタ）アクリルアミド、Ｎ−
Ｎ′−ジメチル（メタ）アクリルアミド、アクリルニト
リル、メチルメタアクリレート等のノニオン性ビニル単
量体、（メタ）アクリル酸、２−アクリルアミド−２−
メチルプロパンスルホン酸またはそれらの塩から選ばれ
るアニオン性ビニル単量体、または上記一般式（ａ）で
表されるカチオン性ビニル単量体を、単独重合するか、
またはこれらビニル単量体の二種以上を共重合させて得
られる水溶性ポリマーを、水溶液中に０．１〜１０重量
％含有するポリマー水溶液。 （Ｃ）水溶性ポリマー水分散液； 一般式（ｂ）（化２） 【化２】 （式中、Ａは酸素原子またはＮＨ；Ｚは炭素数１〜４の
アルキレン基または炭素数２〜４のヒドロキシアルキレ
ン基；Ｒ1 は水素またはメチル基；Ｒ2 、Ｒ4 はメチル
基またはエチル基；Ｒ3 は（ＣＨ2 ）n ＣＨ3 （ｎは３
〜９）またはＣ2Ｈ4 Ｃ6 Ｈ5 ；Ｘ- は塩を形成する陰
イオンを表す）で表されるカチオン性ビニル単量体の単
独重合、またはこれらカチオン性ビニル単量体の一種あ
るいは二種以上と（メタ）アクリルアミドとの共重合
を、生成する重合体を溶解しない無機塩水溶液中で、か
つこの無機塩水溶液に溶解可能な上記一般式（ａ）で表
されるカチオン性ビニル単量体から誘導されるカチオン
性水溶性重合体分散剤の共存下で行って得られる水溶性
ポリマーを１〜３０重量％含有する水溶性ポリマー水分
散液。(1) 50 to 99% by weight of the following water-in-oil polymer emulsion (A), (2) 1 to 50% by weight of the following polymer aqueous solution (B) and / or the following water-soluble polymer dispersion (C). And (3) a liquid polymer emulsion composition comprising 0.1 to 20% by weight of an inorganic salt selected from ammonium sulfate, sodium sulfate, sodium dihydrogen phosphate, sodium chloride or a mixture of two or more of these inorganic salts. object. (A) Water-in-oil polymer emulsion; General formula (a) (Chemical formula 1) (In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 4 carbon atoms.
R 3 and R 4 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms; X − represents an anion forming a salt). Cationic vinyl monomer, or a nonionic vinyl monomer selected from (meth) acrylamide, N-N'-dimethyl (meth) acrylamide, acrylonitrile, and methylmethacrylate, or (meth) acrylic acid, 2- Homopolymerization of an anionic vinyl monomer selected from acrylamido-2-methylpropanesulfonic acid or a salt thereof in the presence of water, a hydrophobic organic liquid or a surfactant, or two kinds of these vinyl monomers A water-in-oil polymer emulsion obtained by copolymerizing the above, wherein the polymer concentration is 20 to 70% by weight and the hydrophobic organic liquid concentration is A water-in-oil polymer emulsion containing 10 to 50% by weight and a surfactant concentration of 8% by weight or less. (B) Polymer aqueous solution; (meth) acrylamide, N-
Nonionic vinyl monomers such as N′-dimethyl (meth) acrylamide, acrylonitrile, and methylmethacrylate, (meth) acrylic acid, 2-acrylamido-2-
By homopolymerizing an anionic vinyl monomer selected from methylpropanesulfonic acid or salts thereof, or a cationic vinyl monomer represented by the general formula (a), or
Alternatively, an aqueous polymer solution containing 0.1 to 10% by weight of a water-soluble polymer obtained by copolymerizing two or more of these vinyl monomers. (C) Aqueous dispersion of water-soluble polymer; General formula (b) (Chemical Formula 2) (In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 and R 4 are a methyl group or ethyl. Group; R 3 is (CH 2 ) n CH 3 (n is 3
To 9) or C 2 H 4 C 6 H 5 ; X − represents an anion forming a salt), a homopolymerization of a cationic vinyl monomer, or one of these cationic vinyl monomers, or Copolymerization of two or more kinds with (meth) acrylamide is carried out in an aqueous solution of an inorganic salt that does not dissolve the resulting polymer, and is soluble in the aqueous solution of the inorganic salt. A water-soluble polymer aqueous dispersion containing 1 to 30% by weight of a water-soluble polymer obtained in the presence of a cationic water-soluble polymer dispersant derived from a polymer.
成物を主成分とする高分子凝集剤。2. A polymer flocculant containing the polymer emulsion composition according to claim 1 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23728393A JPH0762254A (en) | 1993-08-31 | 1993-08-31 | Polymer emulsion composition and polymer flocculant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23728393A JPH0762254A (en) | 1993-08-31 | 1993-08-31 | Polymer emulsion composition and polymer flocculant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0762254A true JPH0762254A (en) | 1995-03-07 |
Family
ID=17013097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23728393A Pending JPH0762254A (en) | 1993-08-31 | 1993-08-31 | Polymer emulsion composition and polymer flocculant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0762254A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09276605A (en) * | 1996-04-16 | 1997-10-28 | Kurita Water Ind Ltd | Water-in-oil type emulsion flocculant |
| US5696228A (en) * | 1996-10-03 | 1997-12-09 | Cytec Technology Corp. | Process for producing substantially dry polymer particles from aqueous dispersions |
| US5792366A (en) * | 1996-10-03 | 1998-08-11 | Cytec Technology Corp. | Aqueous dispersions |
| US5843320A (en) * | 1996-10-03 | 1998-12-01 | Cytec Technology Corp. | Aqueous dispersions |
| US5919854A (en) * | 1996-10-03 | 1999-07-06 | Cytec Technology Corp. | Process for preparing aqueous dispersions |
| US6608124B1 (en) | 1996-10-03 | 2003-08-19 | Cytec Technology Corp. | Aqueous dispersions |
| US6664326B1 (en) | 1996-10-03 | 2003-12-16 | Cytec Technology Corp. | Aqueous dispersions |
| US6702946B1 (en) | 1996-10-03 | 2004-03-09 | Cytec Technology Corp. | Aqueous dispersions |
| JP2009501820A (en) * | 2005-07-21 | 2009-01-22 | チバ ホールディング インコーポレーテッド | Polyelectrolyte composites as thickeners for high ionic strength salt solutions |
| JP2011502186A (en) * | 2007-10-23 | 2011-01-20 | アシュランド・ライセンシング・アンド・インテレクチュアル・プロパティー・エルエルシー | Inversely emulsified polymer containing polymer coagulant |
| JP2012172272A (en) * | 2011-02-18 | 2012-09-10 | Hymo Corp | Papermaking method |
| US8480853B2 (en) | 2010-10-29 | 2013-07-09 | Buckman Laboratories International, Inc. | Papermaking and products made thereby with ionic crosslinked polymeric microparticle |
| JP2015006636A (en) * | 2013-06-24 | 2015-01-15 | 友岡化研株式会社 | Production method of water-soluble cation polymer solution and thickening and dewatering method of organic sludge |
| JP2022080874A (en) * | 2020-11-18 | 2022-05-30 | 荒川化学工業株式会社 | Paper-strengthening agent, and paper |
-
1993
- 1993-08-31 JP JP23728393A patent/JPH0762254A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09276605A (en) * | 1996-04-16 | 1997-10-28 | Kurita Water Ind Ltd | Water-in-oil type emulsion flocculant |
| US6664326B1 (en) | 1996-10-03 | 2003-12-16 | Cytec Technology Corp. | Aqueous dispersions |
| US5792366A (en) * | 1996-10-03 | 1998-08-11 | Cytec Technology Corp. | Aqueous dispersions |
| US5843320A (en) * | 1996-10-03 | 1998-12-01 | Cytec Technology Corp. | Aqueous dispersions |
| US5919854A (en) * | 1996-10-03 | 1999-07-06 | Cytec Technology Corp. | Process for preparing aqueous dispersions |
| US6608124B1 (en) | 1996-10-03 | 2003-08-19 | Cytec Technology Corp. | Aqueous dispersions |
| US5696228A (en) * | 1996-10-03 | 1997-12-09 | Cytec Technology Corp. | Process for producing substantially dry polymer particles from aqueous dispersions |
| US6702946B1 (en) | 1996-10-03 | 2004-03-09 | Cytec Technology Corp. | Aqueous dispersions |
| JP2009501820A (en) * | 2005-07-21 | 2009-01-22 | チバ ホールディング インコーポレーテッド | Polyelectrolyte composites as thickeners for high ionic strength salt solutions |
| US8419976B2 (en) | 2005-07-21 | 2013-04-16 | Basf Se | Polyelectrolyte complexes as thickeners for high ionic strength salt solutions |
| JP2011502186A (en) * | 2007-10-23 | 2011-01-20 | アシュランド・ライセンシング・アンド・インテレクチュアル・プロパティー・エルエルシー | Inversely emulsified polymer containing polymer coagulant |
| US8480853B2 (en) | 2010-10-29 | 2013-07-09 | Buckman Laboratories International, Inc. | Papermaking and products made thereby with ionic crosslinked polymeric microparticle |
| JP2012172272A (en) * | 2011-02-18 | 2012-09-10 | Hymo Corp | Papermaking method |
| JP2015006636A (en) * | 2013-06-24 | 2015-01-15 | 友岡化研株式会社 | Production method of water-soluble cation polymer solution and thickening and dewatering method of organic sludge |
| JP2022080874A (en) * | 2020-11-18 | 2022-05-30 | 荒川化学工業株式会社 | Paper-strengthening agent, and paper |
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